Condensation products derived from amines and method of producing them



Patented Oct. 3, 1939 UNITED STATES PATENT OFFICE Hermann Schuette,Mannheim,

Ludwigshaten-on-the-Rhine, Germany,

and liiax Wittwer,

assignors to I. G. Farbenindustrie Aktiengeselischatt,Frankiort-on-the-Main, Germany No Drawing. Original Serial No. 16,259.

application April 13, 1935,

Divided and this application February 15, 1939, Serial No. 256,557. InGermany April 19, 1934 9 Claims.

The present application is a divisional application of our copendingapplication Ser. No. 16,259, filed April 13, 1935 and relates to new,valuable, condensation products which are suitable as assistants for thetextile and related industries, and a process of producing same.

We have found that valuable, water-soluble (which term includescolloidally soluble) con densation products can be obtained by reactingan organic amine containing at least one reactive hydrogen atom in themolecule, with a compound capable of acting as an alkylene oxide freefrom other oxygen than the oxide oxygen and containing at least threecarbon atoms in the molecule and efiecting a water-solubilizing step.The term compound capable of reacting as an alkylene oxide free fromother oxygen than the oxide oxygen and containing at least three carbonatoms in the molecule comprises alkylene oxides with the said number ofcarbon atoms themselves, furthermore 1.2-propylene glycol and its higherhomologues.

As amines suitable as initial material there may be mentioned forexample butylamine, octylamine, cetylamine, oleylamine, aniline,phenylenediamine, benzidine, or naphthylamine and aminonaphthols. Thesaid amines may also contain substituents, such as, for example, halogenatoms, nitro or sulphonic groups.

The water-solubilizing step which is to be applied to the productsconsists preferably in reacting them with a compound capable of reactingas a polyhydric alcohol of low molecular weight, usually with from 2 to4, preferably with 2 carbon atoms per molecule, and containing onehydroxyl group per each carbon atom. As such compounds may be mentionedethylene glycol, or ethylene oxide which are preferably employed ingreat excess; polyglycol ether radicles, such as, for example,diethylene, triethylene or tetraethylene glycol or polyglycerine, mayalso be introduced. In many cases it is advantageous to cause several ofthe said compounds to enter into reaction, preferably in several stages.I

If the said preferred form of effecting the water-solubilizing step isemployed, the sequence of the condensation with the compound capable ofreacting as an alkylene oxide free from other oxygen than the oxideoxygen and containing at least 3 carbon atoms in the molecule and thesaid water-solubilizing step may be as desired. In other words, theentire process consists in acting on the amines containing at least onereactive hydrogen atom in any desired order ing the polyhydric alcoholsof low molecular weight to react with the amines, the resultingcondensation products thereupon being reacted with the alkylene oxidescontaining at least three carbon atoms in the molecule. When theresulting condensation products are not sufliciently soluble in water,they may be readily converted into a water-soluble condition bysulphonation or by the introduction of other groups capable of renderingthem water-soluble.

In the condensation of the amines containing at least one reactivehydrogen atom per molecule with the compound capable of reacting as analkylene oxide containing at least three carbon atoms, preferablyseveral molecular proportions of the latter (for example of propyleneoxide) are used for each molecular proportion of the initial material.The reaction is preferably effected in the presence of condensingagents, such as for example caustic soda solution, caustic potashsolution, sodium ethylate, sodium acetate or activated bleaching earths,advantageously at elevated temperature and if desired under pressure.Instead of the said alkylene oxides, compounds which act in the sameway, such as 1.2-propyleneglyco1, may be employed. The alkylene oxide orlike molecules probably add on to each other with the formation ofether-like chains of high molecular weight and one or more of thesechains enter into the molecule depending on the initial materialsemployed.

The condensation with the compounds capable of reacting as polyhydricalcohols of low molecular weight is also advantageously carried out inthe presence of the said condensing agents at elevated temperature andit is also preferable to work under increased pressure.

If such amines containing reactive hydrogen are employed as are highmolecular (which contain at least 6, preferably at least 8,advantageously from 8 to 18 carbon atoms per molecule) thewater-solubilizing step may consist in a sulphonation; this is effectedin the usual manner by treating the products with sulphuric acid, oleum,sulphur trioxide or chlor-sulphonic acid, if desired in the presence ofsolvents or diluents or while adding compounds capable of withdrawingwater.

The products obtainable according to the present invention are suitable,for example, as wetting, washing, dispersing, levelling, softening andlike agents in the textile, leather, paper, lacquer, rubber and likeindustries, they are also capable of employment with advantage in thecosmetic and pharmaceutical industries in many cases. They have inparticular a high protective colloid actionand, for example, prevent toa great extent the separation of calcium soaps when working with soapsin hard water. Many of the products are also suitable as superfattingagents for soaps. The products may be advantageously employed togetherwith other substances usually employed in the textile, leather, paperand like industries, for example, with soaps, Turkey red oils, truealiphatic sulphonic acids of high molecular weight, alkylated aromaticsulphonic acids, organic solvents, such as cyclohexanol, cyclohexanone,benzyl alcohol and carbon tetrachloride, or

salts, such as Glaubers salt, alkali metal phosphates, waterglass andborates. They may also be employed together with oxidizing and reducingagents, such as sodium hypochlorite and sodium hydrosulphite, or withvegetable mucilages, glue, starch or ethylene oxide polymerizationproducts.

The following examples will further illustrate the nature of thisinvention but the invention is not restricted to these examples. byweight.

Example 1 1 molecular proportion of dodecylamine is caused to react with2 molecular proportions of epichlorhydrin which are added to thereaction mixture in small portions, 2 molecular proportions of propyleneoxide then being brought into reaction at zero C. in the presence of 0.5per cent of sodium ethylate. The resulting product is especiallysuitable as a superfatting agent for soaps or a substitute for lanoline.

Example 2 1 molecular proportion of cetyl amine is heated in anautoclave under pressure at about 150 C. with 4 molecular proportions ofpropylene oxide and then with from 12 to 16 molecular proportions ofethylene oxide. A water-soluble product is thus obtained which favorsthe formation of level dyeings in acid dyeing of wood.

What we claim is:

1. The process of producing condensation products which comprisesreacting an amine containing at least one reactive hydrogen atom in themolecule with a compound capable of acting as an alkylene oxide freefrom other oxygen than the oxide oxygen and containing at least threecarbon atoms in the molecule, and efifecting a water-solubilizing step.

2. The process of producing condensation products which comprisesreacting an amine containing at least one reactive hydrogen atom in themolecule in any desired sequence with a compound capable of acting as analkylene oxide free from other oxygen than the oxide oxygen andcontaining at least three carbon atoms in the molecule, and a compoundcapable of reacting The parts are as a low molecular polyhydric alcohol,containing one hydroxyl group per each carbon atom.

3. The process of producing condensation products which comprisesreacting an amine containing at least one reactive hydrogen atom in themolecule in any desired sequence with a com pound capable of acting asan alkylene oxide free from other oxygen than the oxide oxygen andcontaining at least three carbon atoms in the molecule, and a compoundcapable of reacting as a polyhydric alcohol with from 2 to 4 carbonatoms per molecule and containing one hydroxyl group per each carbonatom.

4. The process of producing condensation products which comprisesreacting an amine containing at least one reactive hydrogen atom in themolecule in any desired sequence with a compound capable of acting as analkylene oxide free from other oxygen than the oxide oxygen andcontaining at least three carbon atoms in the molecule, and a compoundcapable of reacting as a polyhydric alcohol with from 2 to 4 carbonatoms per molecule and containing one hydroxyl group per each carbonatom and treating the product obtained with a sulphonating agent.

5. The process of producing condensation products which comprisesreacting an amine containing at least 6 carbon atoms and at least onereactive hydrogen atom in the molecule with a compound capable of actingas an alkylene oxide free from other oxygen than the oxide oxygen andcontaining at least three carbon atoms in the molecule, and with asulphonating agent.

6. Condensation products derived from an amine containing at least onereactive hydrogen atom in the molecule and from a compound capable ofacting as an alkylene oxide free from other oxygen than the oxide oxygenand containing at least three carbon atoms in the molecule, andcontaining at least one water-solubilizing group.

7. Condensation products derived from an amine containing at least onereactive hydrogen atom in the molecule, from a compound capable ofacting as an alkylene oxide free from other oxygen than the oxide oxygenand containing at least three carbon atoms in the molecule, and acompound capable of reacting as a low molecular polyhdric alcoholcontaining one hydroxyl group per each carbon atom.

8. Condensation products derived from an amine containing at least onereactive hydrogen atom in the molecule, from a compound capable ofacting as an alkylene oxide free from other oxygen than the oxide oxygenand containing at least three carbon atoms in the molecule, and acompound capable of reacting as a low molecular polyhdric alcoholcontaining one hydroxyl group per each carbon atom, the saidcondensation products containing at least one sulphuric acid derivativegroup selected from the class consisting of the sulphuric ester andsulphonic acid groups.

9. Condensation products derived from an amine containing at least 6carbon atoms and at least one reactive hydrogen atom in the molecule andfrom a compound capable of acting as an alkylene oxide free from otheroxygen than the oxide oxygen and containing at least three carbon atomsin the molecule, and containing at least one sulphuric acid derivativegroup selected from the class consisting of the sulphuric ester andsulphonic acid groups.

HERMANN SCHUET'IE. MAX WI'I'IWER.

